Organic acids and process for preparing same

ABSTRACT

A mixture of polycyclic, aromatic polycarboxylic acids carrying nuclear nitro groups that is substantially soluble in an azeotropic mixture of methyl ethyl ketone and ethanol but substantially insoluble in water, and a process for preparing the mixture of polycyclic, aromatic polycarboxylic acids.

This is a continuation-in-part application of my Application Ser. No. 910,215 filed May 30, 1978 for ORGANIC ACIDS AND PROCESS FOR PREPARING SAME now U.S. Pat. No. 4,334,084, which issued on June 8, 1982.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a mixture of polycyclic, aromatic polycarboxylic acids carrying nuclear nitro groups that is substantially soluble in an azeotropic mixture of methyl ethyl ketone and ethanol but substantially insoluble in water, and a process for preparing the mixture of polycyclic, aromatic polycarboxylic acids.

2. Description of Prior Art

In U.S. Pat. No. 4,052,448 to J. G. Schulz and E. T. Sabourin, there is disclosed a mixture of polycyclic, aromatic polycarboxylic acids carrying nuclear nitro groups that is substantially soluble in a polar solvent but substantially insoluble in water, and a process for preparing the mixture.

SUMMARY OF THE INVENTION

The process defined and claimed herein is directed to an improvement in the process claimed in U.S. Pat. No. 4,052,448. I have found that if in the process of the patent a mixture of two polar solvents, one being methyl ethyl ketone and the other being ethanol, is used in place of methyl ethyl ketone alone or said ethanol alone in recovering the desired mixture of polycyclic, aromatic polycarboxylic acids, an unexpectedly larger amount of polycyclic, aromatic polycarboxylic acids is obtained than when only methyl ethyl ketone or only ethanol is used.

The individual components of the novel mixtures of polycyclic, aromatic polycarboxylic acids obtained herein are believed to be composed of condensed and/or non-condensed benzene rings, with an average number of rings in the individual molecules ranging from 2 to about 10, but generally from 3 to about 8. On the average, the number of carboxyl groups carried by the individual molecules will range from about 4 to about 10, generally from about 6 to about 8, and the average number of nitro groups from about 1 to about 4, generally from about 2 to about 3. The average molecular weight of the mixture will range from about 600 to about 1500, generally from about 700 to about 1000, and the average neutral equivalent will range from about 80 to about 200, generally from about 100 to about 150. A typical analysis of the novel mixture is defined below in Table I in approximate amounts.

                  TABLE I                                                          ______________________________________                                                    Weight Percent                                                                 Broad Range                                                                             Preferred Range                                            ______________________________________                                         Carbon       50 to 60   52 to 56                                               Hydrogen     3 to 5     3.7 to 4.4                                             Nitrogen     3 to 6     4 to 5                                                 Oxygen       25 to 45   30 to 40                                               Sulfur       0.2 to 0.5 0.3 to 0.5                                             Ash          0.1 to 5.0 0.3 to 3.0                                             ______________________________________                                    

The amount of each polar solvent present in the solvent mixture defined above will be that amount just sufficient to form an azeotropic mixture when the solvent mixture is subjected to distillation at ambient pressure. Thus, according to "Azeotropic Data", Advances in Chemistry Series, No. 6, published by the American Chemical Society, Washington, D.C., 1951, an azeotropic mixture of methyl ethyl ketone and ethanol will have a weight ratio of 54:46.

The procedure employed herein preferably follows the procedure defined in U.S. Pat. No. 4,052,448. Thus there is introduced into a reactor an aqueous solution of nitric acid and a carbonaceous material. The nitric acid can have a concentration of about 5 to about 90 percent, but preferably will be in the range of about 10 to about 70 percent. The carbonaceous material is preferably a solid in the form of a slurry, for example, an aqueous slurry containing the carbonaceous material in particulate form and from about 50 to about 90 weight percent of water.

The solid carbonaceous material that can be used herein can have the following composition on a moisture-free basis:

                  TABLE II                                                         ______________________________________                                                    Weight Percent                                                                 Broad Range                                                                             Preferred Range                                            ______________________________________                                         Carbon       45 to 95   60 to 92                                               Hydrogen     2.5 to 7   4 to 6                                                 Oxygen       2.0 to 45   3 to 25                                               Nitrogen     0.75 to 2.5                                                                               0.75 to 2.5                                            Sulfur       0.3 to 10  0.5 to 6                                               ______________________________________                                    

The carbon and hydrogen content of the carbonaceous material will reside primarily in multi-ring aromatic compounds (condensed and/or uncondensed), heterocyclic compounds, etc. Oxygen and nitrogen are believed to be present primarily in chemical combination. Some of the sulfur is believed to be present in chemical combination with the aromatic compounds and some in chemical combination with inorganic elements associated therewith, for example, iron and calcium.

In addition to the above, the solid carbonaceous material being treated herein will also contain solid, primarily inorganic, compounds which will not be converted to the desired organic mixture claimed herein, which are termed "ash", and are composed chiefly of compounds of silicon, aluminum, iron and calcium, with smaller amounts of compounds of magnesium, titanium, sodium and potassium. The ash content of the carbonaceous material treated herein will amount to less than about 50 weight percent, based on the moisture-free carbonaceous material, but, in general, will amount to about 0.1 to about 30 weight percent, usually about 0.5 to about 20 weight percent.

Anthracitic, bituminous and subbituminous coal, lignitic materials, and other types of coal products referred to in ASTM D-388 are exemplary of the solid carbonaceous materials which can be treated in accordance with the process defined herein to produce the claimed organic mixture. Some of these carbonaceous materials in their raw state will contain relatively large amounts of water. These can be dried prior to use herein. The carbonaceous material, prior to use, is preferably ground in a suitable attrition machine, such as a hammermill, to a size such that at least about 50 percent of the carbonaceous material will pass through a 40-mesh (U.S. Series) sieve. As noted, the carbonaceous material is slurried in a suitable carrier, preferably water, prior to reaction with nitric acid. If desired, the carbonaceous material can be treated, prior to reaction herein, using any conventional means, to remove therefrom any materials forming a part thereof that will not be converted in reaction with nitric acid herein.

The reactant mixture in the reactor is stirred while being maintained at a temperature of about 15° to about 200° C., preferably about 50° to about 100° C., and a pressure of about atmospheric to about 1000 psig (about atmospheric to about 70 kg/cm²), preferably about atmospheric to about 500 psig (about atmospheric to about 35 kg/cm²) for about 0.5 to about 15 hours, preferably about two to about six hours. In order to obtain the desired mixture herein without losing appreciable amounts of carboxyl and/or nitro groups on the acids that are formed during the oxidation and to obtain the desired acids in high yields in the reactor, it is absolutely critical that the reaction conditions therein, namely nitric acid concentration, temperature, pressure and reaction time, be so correlated to minimize and, preferably, to avoid decarboxylation and denitrofication. Gaseous products, such as nitrogen oxides, can be removed from the reactor as they are formed.

The reaction product is removed from the reactor upon completion of the reaction. The reaction product is soluble in, or reactable with, sodium hydroxide. At this point it is necessary to separate the oxidized product from the water and nitric acid associated therewith. This separation must be accomplished in a manner so that the carboxyl and nitro groups are not removed from the acid product. Distillation for the removal of water will not suffice, because under the conditions required for such separation, a significant loss of carboxyl groups and nitro groups would occur. Accordingly, it has been found that a mechanical separation will suffice. The reaction product is therefore led to a first separator which can be, for example, a filter or a centrifuge.

The solids that are recovered in the first separator, also soluble in sodium hydroxide, are led to a second separator wherein they are subjected to extraction with an azeotropic mixture of polar solvents defined above, that is, methyl ethyl ketone and ethanol, introduced therein by any convenient entry line. Such separation can be carried out at a temperature of about 20° to about 100° C., preferably about 25° to about 50° C., and a pressure of about atmospheric to about 500 psig (about atmospheric to about 35 kg/cm²), preferably about atmospheric to about 100 psig (about atomospheric to about 7 kg/cm²). The amount of the mixture of polar solvents used herein to recover the desired acid mixture can be varied over a wide range in any amount sufficient to extract the desired acid mixture from the solid mixture in the first extractor. Thus, the weight ratio of total polar solvents to solid acid mixture can be in the range of about 1:1 to about 10:1, preferably about 2:1 to about 5:1.

The solid material, insoluble in the mixture of solvents, is removed from the second separator by one line, and the polar solution of the novel acid mixture by another line. The polar solution is then led to a drier wherein the mixture of polar solvents is separated therefrom by one line and the desired novel polar-soluble, water-insoluble polyaromatic, polycarboxylic acid mixture claimed herein is recovered by another line. As before, the acid mixture in the drier must be treated by so correlating the conditions to remove the mixture of polar solvents therefrom in such manner so as to minimize and, preferably, avoid, decarboxylation and denitrofication. The temperature can be in the range of about 10° to about 100° C., preferably about 20° to about 50° C., the pressure about 10 millimeters of mercury to about atmospheric, preferably about 30 millimeters of mercury to about atmospheric, for about 0.5 to about 24 hours, preferably about one to about five hours.

The filtrate obtained in the first separator is removed therefrom and will contain water, nitric acid and most of the inorganic material (ash) that was present in all the carbonaceous charge. In addition there can also be present other oxidized material, which are primarily organic acids soluble in polar solvents and in water.

DESCRIPTION OF PREFERRED EMBODIMENTS

A North Dakota Lignite, analyzing as follows on a substantially moisture-free basis, was subjected to oxidation using: 70 weight percent aqueous nitric acid as the oxidant; 65.03 weight percent carbon; 4.0 weight percent hydrogen; 27.0 weight percent oxygen; 0.92 weight percent sulfur; 0.42 weight percent nitrogen; and 0.04 weight percent moisture. The ash was further analyzed and found to contain 43 weight percent oxygen; 7.8 weight percent sulfur; and the remainder, metals. The weight ratio of lignite to nitric acid (as 100 percent nitric acid) and water in the reactor was 1:1:1. The reaction mixture was stirred and maintained at a temperature of 80° C. and a pressure of 800 psig (55 kg/cm²) for five hours. Nitrogen oxides were permitted to escape from the reaction zone as they evolved.

At the end of the reaction period the product slurry was withdrawn from the reaction zone and filtered to obtain a solids fraction and a filtrate. Portions (100 grams) of the solids fraction were each dissolved in a number of polar solvents with the following results:

                  TABLE III                                                        ______________________________________                                                            Solubility Data                                                                      Wt %     Wt %                                         Solvent        Grams     Soluble  Insoluble                                    ______________________________________                                         Ethanol        100       70.0     30.0                                         Methyl Ethyl Ketone                                                                           100       39.2     60.8                                         ______________________________________                                    

Another portion (100 grams) of the solids was dissolved in a mixture of methyl ethyl ketone and ethanol, wherein the components thereof were present in an amount sufficient to form an azeotropic mixture, with the following results:

                                      TABLE IV                                     __________________________________________________________________________     Solvent Solution         Solubility Data                                                           Weight                                                                         Ratio:                                                     Total               Ketone/                                                                             Wt % Soluble                                                                             Wt % Insoluble                              Grams                                                                              Ketone     Alcohol                                                                             Alcohol*                                                                            Found                                                                              Expected**                                                                           Found                                                                              Expected**                              __________________________________________________________________________     100 Methyl Ethyl Ketone                                                                       Ethanol                                                                             54.46                                                                               89.3                                                                               51.5  10.7                                                                               48.5                                    __________________________________________________________________________      *Values taken from "Azeotropic Data", Advances in Chemistry Series, No. 6      published by the American Chemical Society, Washington, D.C., 1951.            **Expected values based on the solubilities obtained from individual pola      solvents in Table III.                                                   

Comparison of the data obtained in Table IV with that of Table III clearly illustrates the uniqueness of the invention claimed herein. When the solvent solution contained both methyl ethyl ketone and ethanol, unexpectedly larger amounts of polycyclic aromatic polycarboxylic acids were obtained than would have been predicted on the basis of the results obtained with either of the polar solvents alone. An additional advantage is obtained herein because the mixture of polar solvents form an azeotropic mixture. Thus, when the polar solvent solution containing the desired acid mixture dissolved therein is subjected to drying conditions, as set forth hereinabove, to separate the polar solvents from the desired acid mixture, the solvent mixture will come off cleanly as a single solution which can then be recycled to the second separator defined above for recovery of additional acid mixture. Not only is the separation of solvent solution from the acid mixture thereby facilitated, but since the ratios of components present in the solvent solution will remain constant, the amount of acid mixture recovered will also remain constant.

Since the novel mixtures herein have abundant functionality in both carboxyl and nitro groups, it is apparent that the mixtures lend themselves to many known chemical reactions, for example: esterification of the carboxyl groups; hydrogenation of the nitro groups to amines; etc. Thus, the novel mixtures defined herin are effective blowing agents for the purpose of incorporating the same in well-known resins, such as polyethylene, to permanently increase the volume of the resin as shown in U.S. Pat. No. 4,101,469 of Schulz et al., dated July 18, 1978.

Obviously many modifications and variations of the invention, as herein above set forth, can be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims. 

We claim:
 1. In a process for preparing a mixture of polycyclic, aromatic polycarboxylic acids carrying nuclear nitro groups that is soluble in a mixture consisting essentially of methyl ethyl ketone and ethanol but substantially insoluble in water which consists essentially in subjecting a slurry containing coal to reaction with aqueous nitric acid having a concentration of about 5 to about 90 percent at a temperature of about 15° to about 200° C. for about 0.5 to about 15 hours and mechanically separating the solids in the resulting slurry, the improvement which consists essentially in extracting said separated solids with a mixture consisting essentially of methyl ethyl ketone and ethanol in amounts sufficient to form an azeotropic mixture and then separating said methyl ethyl ketone and said ethanol from the extract to obtain said mixture of polycyclic, aromatic polycarboxylic acids.
 2. The process of claim 1 wherein the weight ratio of total polar solvent to said separated solids is about 1:1 to about 10:1.
 3. The process of claim 1 wherein the weight ratio of total polar solvent to said separated solids is about 2:1 to about 5:1.
 4. The process of claim 1 wherein the nitric acid has a concentration of about 10 to about 70 percent and the reaction is carried out at a temperature of about 50° to about 100° C. for about two to about six hours.
 5. The process of claim 1 wherein the mechanical separation is effected by filtration.
 6. The process of claim 1 wherein the separation of polar solvents is effected by subjecting the extract to drying.
 7. The process of claim 1 wherein the recovered methyl ethyl ketone and ethanol are recycled to the extraction stage.
 8. The process of claim 1 wherein the coal is lignite. 